Fungicides

ABSTRACT

Fungicidal compounds of the formula (I): ##STR1## in which A and B are independently H, fluoro, chloro, bromo, C 1-4  alkyl, C 1-4  alkoxy or halo(C 1-4 )alkyl provided that both are not H; D and E are independently H or fluoro; R 1  is H, C 1-4  alkyl or C 1-4  alkoxy; R 2  is CC 1-4  alkyl, C 1-4  alkoxy or optionally substituted phenyl, or R 1  and R 2  together with the nitrogen atom to which they are attached join to form a morpholine, piperidine, pyrrolidine or azetidine ring which is optionally substituted with C 1-4  alkyl; R 3  is H; R 4  is trichloromethyl, C 2-8  alkyl (optionally substituted with halogen, C 1-8  alkoxy or R&#39;S(O) in which R&#39; is C 1-4  alkyl, C 2-4  alkenyl or C 2-4  alkynyl and n is 0, 1 or 2), cyclopropyl (optionally substituted with halogen or C 1-4  alkyl), C 2-8  alkenyl, C 2-8  alkynyl, C 1-8  alkoxy, mono- or di(C 1-4 )alkyl- amino or the group, R&#34;ON═C(CN) in which R&#34; is C 1-4  alkyl, or R 3  and R 4  together with the group C(O)N to which they are attached join to form an azetidin-2-one ring which is optionally substituted with halogen or C 1-4  alkyl; and X and Y are independently oxygen or sulphur.

This is a division of application Ser. No. 07/473,677, filed Feb. 2,1990, U.S. Pat. No. 4,999,381.

This invention relates to novel fungicidal acylaminobenzamides, toprocesses for preparing them, to fungicidal compositions containing themand to methods of using them to combat fungi, especially fungalinfections of plants.

Acknowledgement is made of UK Application No. 42454/77 from which U.S.Pat. No. 4282218, for example, claims priority and of EP-A-0127990. Theformer describes acylanilides which have antiandrogenic properties andthe latter describes aniline derivatives which have fungicidalproperties.

According to the present invention there is provided a compound of theformula (I): ##STR2## in which A and B are independently H, fluoro,chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy or halo(C₁₋₄)alkyl provided thatboth are not H; D and E are independently H or fluoro; R¹ is H, C₁₋₄alkyl or C₁₋₄ alkoxy; R² is C₁₋₄ alkyl, C₁₋₄ alkoxy or optionallysubstituted phenyl, or R¹ and R² together with the nitrogen atom towhich they are attached join to form a morpholine, piperidine,pyrrolidine or azetidine ring which is optionally substituted with C₁₋₄alkyl; R³ is H; R⁴ is trichloromethyl, C₂₋₈ alkyl (optionallysubstituted with halogen, C₁₋₈ alkoxy or R'S(O)_(n) in which R' is C₁₋₄alkyl, C₂₋₄ alkenyl or C₂₋₄ alkynyl and n is 0, 1 or 2), cyclopropyl(optionally substituted with halogen or C₁₋₄ alkyl), C₂₋₈ alkenyl, C₂₋₈alkynyl, C₂₋₈ alkoxy, mono- or di(C₁₋₄)- alkylamino or the group,R"ON═C(CN) in which R" is C₁₋₄ alkyl, or R³ and R⁴ together with thegroup C(O)N to which they are attached join to form an azetidin-2-onering which is optionally substituted with halogen or C₁₋₄ alkyl; and xand Y are independently oxygen or sulphur.

Alkyl groups and the alkyl moiety of other alkyl-containing groups canbe in the form of straight or branched chains. Examples are methyl,ethyl, propyl (n-and iso-propyl), butyl (n-, sec, iso- and t-butyl),1,1-dimethylpropyl and 1,1-dimethylbutyl. Alkenyl and alkynyl groups canalso be in the form of straight or branched chains. Examples are1,1-dimethylbut-3-enyl and 1,1-dimethylprop-2-ynyl.

Halogen includes fluorine, chlorine and bromine.

Optional substituents of phenyl include: halogen, C₁₋₄ alkyl (forexample, methyl), C₁₋₄ alkoxy (for example methoxy), C₁₋₄ alkylthio (forexample methylthio), trifluoromethyl, trifluoromethoxy, nitro, cyano,C₁₋₄ alkoxycarbonyl, amino and mono- and di(C₁₋₄)alkylamino.

In one aspect the invention provides a compound of formula (I) in whichA and B are independently H, fluoro, chloro or bromo provided that bothare not H; D and E are both H; R¹ is hydrogen or C₁₋₄ alkyl; R² is C₁₋₄alkyl, C₁₋₄ alkoxy or phenyl, or R¹ and R² together with the nitrogenatom to which they are attached join to form a morpholine, piperidine,pyrrolidine or azetidine ring; R³ is hydrogen; R⁴ is C₃₋₆ alkyl(optionally substituted with halogen, methoxy, methylthio ormethylsulphonyl), cyclopropyl (optionally substituted with methyl), C₃₋₆alkenyl, C₃₋₆ alkynyl, C₁₋₄ alkoxy or the group CH₃ ON═C(CN); and X andY are both oxygen.

In another aspect the invention provides a compound of formula (I) inwhich A is chloro; B, D and E are all H; R¹ is hydrogen, methyl orethyl; R² is methyl, ethyl or phenyl, or R¹ and R² together with thenitrogen atom to which they are attached join to form a morpholine orpiperidine ring; R³ is hydrogen; R⁴ is C₃₋₄ alkyl (for exampleiso-propyl or t-butyl) or cyclopropyl; and X and Y are both oxygen.

In yet another aspect the invention provides a compound of formula (I)in which A is chloro; B, D and E are all H; R¹ and R² are independentlymethyl or ethyl (but suitably both methyl or both ethyl) or togetherwith the nitrogen atom to which they are attached join to form amorpholine or piperidine ring; R³ is hydrogen; R⁴ is iso-propyl, t-butylor cyclopropyl; and X and Y are both oxygen.

In yet another aspect the invention provides a compound of the formula(I.1): ##STR3## in which A and B are independently chloro, bromo ormethyl or B is H; and z is fluoro, chloro, bromo, methyl, ethyl ormethoxy. Amongst these compounds are to be noted those in which B is Hand those in which A and B are both chloro or both methyl. Compounds ofparticular interest are those in which A is chloro; B is H; and Z hasany of the meanings given above; and also those in which A is chloro orbromo; B is H, or A and B are both chloro; and Z is methyl.

The invention is illustrated by the compounds listed in Tables I, II andIII which follow.

                                      TABLE I                                     __________________________________________________________________________     ##STR4##                                                                     Compound                                                                      No.   R.sup.1                                                                            R.sup.4                                                                              R.sup.3                                                                         R.sup.4       mpt (°C.)                            __________________________________________________________________________     1    CH.sub.3                                                                           CH.sub.3                                                                             H (CH.sub.3).sub.2 CH                                                                         182-184                                      2    C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H (CH.sub.3).sub.2 CH                                                                         154-157                                      3    (CH.sub.2).sub.2 O(CH.sub.2).sub.2                                                        H (CH.sub.3).sub.2 CH                                                                         180-182                                      4    (CH.sub.2).sub.5                                                                          H (CH.sub.3).sub.2 CH                                                                         182-184                                      5    CH.sub.3                                                                           CH.sub.3                                                                             H (CH.sub.3).sub.3 C                                                                          202-203                                      6    CH.sub.3                                                                           CH.sub.3                                                                             H                                                                                ##STR5##     179-180                                      7    C.sub.2 H.sub.5                                                                    H      H (CH.sub.3).sub.2 CH                                                                         189-190                                       8   H    C.sub.6 H.sub.5                                                                      H (CH.sub.3).sub.2 CH                                                                         223-224                                      9    CH.sub.3                                                                           CH.sub.3                                                                             H Cl.sub.3 C    185-186                                     10    CH.sub.3                                                                           CH.sub.3                                                                             H ClCH.sub.2 (CH.sub.3).sub.2 C                                                               179-181                                      11*  CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.2 C(CH.sub.3).sub.2                                                                    122-123                                     12    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 S(CH.sub.3)CH                                                                      158-161                                     13    CH.sub.3                                                                           CH.sub.3                                                                             H                                                                                ##STR6##     155-156                                     14    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                        155-156                                     15    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 CH.sub.2 CH.sub.2 (CH.sub.3).sub.2 C                                               125-126                                     16    CH.sub.3                                                                           CH.sub.3                                                                             H Br(CH.sub.3).sub.2 C                                                                        181.5-182                                   17    CH.sub.3                                                                           CH.sub.3                                                                             H Cl(CH.sub.3).sub.2 C                                                                        168-169                                     18    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.2 CHCH.sub.2 (CH.sub.3).sub.2 C                                                        120-121.5                                 19    CH.sub.3                                                                           CH.sub.3                                                                             H (Cl).sub.2 CH(CH.sub.3).sub.2 C                                                             180-181                                     20    CH.sub.3                                                                           CH.sub.3                                                                             H (CH.sub.3).sub.3 CO                                                                         206-207                                     21    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 O(CH.sub.3).sub.2 C                                                                141-143                                     22    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 S(CH.sub.3).sub.2 C                                                                133.5-135                                   23    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 SO.sub.2 (CH.sub.3).sub.2 C                                                        169-170                                     24    CH.sub.3                                                                           CH.sub.3                                                                             H (CH.sub.3).sub.2 N                                                                          125-126                                     25    CH.sub.3                                                                           CH.sub.3                                                                             H (CH.sub.3).sub.3 CCH.sub.2                                                                    194-195.5                                 26    CH.sub.3                                                                           CH.sub.3                                                                             H HCC(CH.sub.3).sub.2 C                                                                       179-181                                     27    CH.sub.3                                                                           CH.sub.3                                                                             H BrCH.sub.2 (Br).sub.2 C                                                                     192.5-193.3                                 28    CH.sub.3                                                                           CH.sub.3                                                                             H BrCH.sub.2 (Br)(CH.sub.3)C                                                                  190                                         29    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H (CH.sub.3).sub.3 C                                                                          151-153                                     30    CH.sub.3 CH.sub.2                                                                  CH.sub.3 CH.sub.2                                                                    H (CH.sub.3).sub.3 C                                                                          161-163                                     31    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H (CH.sub.3).sub.3 C                                                                          139-141                                     32    (CH.sub.2).sub.4                                                                          H (CH.sub.3).sub.3 C                                                                          173-174                                     33    (CH.sub.2).sub.3                                                                          H (CH.sub.3).sub.3 C                                                                          185-187                                     34    CH.sub.3                                                                           CH.sub.3 CH.sub.2 CH.sub.2                                                           H (CH.sub.3).sub.3 C                                                                          175-176                                     35    CH.sub.3                                                                           CH.sub.3 O                                                                           H (CH.sub.3).sub.3 C                                                                          Oil                                         36    CH.sub.3                                                                           CH.sub.3                                                                             H (Cl).sub.2 (CH.sub.3)C                                                                      154.5-156.5                                 37    CH.sub.3                                                                           CH.sub.3                                                                             H                                                                                ##STR7##     128-129                                     38    CH.sub.3                                                                           CH.sub.3                                                                             H F(CH.sub.3).sub.2 C                                                                         125-128                                     39    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.2 CH(CH.sub.3).sub.2 C                                                               137-139                                     40    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 OCH.sub.2 (CH.sub.3).sub.2 C                                                       101-103                                     41    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 SCH.sub.2 (CH.sub.3).sub.2 C                     42    CH.sub.3                                                                           CH.sub.3                                                                             H FCH.sub.2 (CH.sub.3).sub.2 C                                                                152-154                                     43    CH.sub.3                                                                           CH.sub.3                                                                             H F.sub.2 CH(CH.sub.3).sub.2 C                              44    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 CHCH(CH.sub.3).sub.2 C                           45    CH.sub. 3                                                                          CH.sub.3 CH.sub.2                                                                    H Cl(CH.sub.3).sub.2 C                                                                        108-111                                     46    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H Br(CH.sub.3).sub.2 C                                                                        133-135                                     47    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H F(CH.sub.3).sub.2 C                                                                         oil                                         48    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H CH.sub.3 O(CH.sub.3).sub.2 C                                                                136-138                                     49    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H ClCH.sub.2 (CH.sub.3).sub.2 C                             50    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H (CH.sub.3).sub.2 CH                                       51    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H                                                                                ##STR8##                                                 52    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                        130-132                                     53    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    CH.sub.2 C(CH.sub.3).sub.2                                  54    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H (CH.sub.3).sub.2 N                                        55    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H CH.sub.2 CHCH.sub.2 (CH.sub.3).sub.2 C                    56    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H (CH.sub.3).sub.3 CO                                       57    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H Cl(CH.sub.3).sub.2 C                                      58    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H Br(CH.sub.3).sub.2 C                                      59    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H F(CH.sub.3).sub.2 C                                       60    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H CH.sub.3 O(CH.sub.3).sub.2 C                              61    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H ClCH.sub.2 (CH.sub.3).sub.2 C                             62    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H (CH.sub.3).sub.2 CH                                       63    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H                                                                                ##STR9##                                                 64    CH.sub.3                                                                           (CH.sub.3).sub.2 CH                                                                  H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                      65    CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                    H CH.sub.2 CH(CH.sub.3).sub.2 C                                                               111-113                                     66    CH.sub.3                                                                           CH.sub.3                                                                             H HCCCH.sub.2 (CH.sub.3).sub.2 C                                                              154-155                                     67    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.3 CHCHCH.sub.2 (CH.sub.3).sub.2 C                                                    120 (dec.)                                  68    CH.sub.3                                                                           CH.sub.3                                                                             H CH.sub.2 CHCH.sub. 2 CH.sub.2 (CH.sub.3).sub.2                                              95-96                                       __________________________________________________________________________     *Compound No 11 has the formula:                                              ##STR10##                                                                

                                      TABLE II                                    __________________________________________________________________________     ##STR11##                                                                    Compound                                                                            R.sup.1                                                                          R.sup.2                                                                             R.sup.3                                                                         R.sup.4    A   B  D E mpt (°C.)                       __________________________________________________________________________     1    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CH.sub.3 O                                                                        H  H H 143-144                                 2    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          H  H H 183-185                                 3    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Br  H  H H 219-222                                 4    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       F   H  H H 125-130                                 5    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Cl  Cl H H 187-188                                 6    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       F   F  F F 187-189                                  7   CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CF.sub.3                                                                          H  H H 198.7-199.6                             8    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                     F   H  H H 110-113                                 9    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                     F   H  H H Gum                                    10    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          CH.sub.3                                                                         H H                                        11    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       F   F  H H                                        12    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Cl  F  H H                                        13    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          F  H H                                        14    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          Cl H H                                        15    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Br  F  H H                                        16    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Cl  Br H H                                        17    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Cl  H  F H                                        18    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Cl  H  H F                                        19    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       Br  H  F H                                        20    CH.sub.3                                                                         CH.sub.3                                                                            H (CH.sub.3).sub.3 C                                                                       CF.sub.3                                                                          F  H H                                        21    CH.sub.3                                                                         CH.sub.3                                                                            H Cl(CH.sub.3).sub.2 C                                                                     Cl  Cl H H                                        22    CH.sub.3                                                                         CH.sub.3                                                                            H Br(CH.sub.3).sub.2 C                                                                     Cl  Cl H H                                        23    CH.sub.3                                                                         CH.sub.3                                                                            H F(CH.sub.3).sub.2 C                                                                      Cl  Cl H H                                        24    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 O(CH.sub.3).sub.2 C                                                             Cl  Cl H H                                        25    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                     Cl  Cl H H                                        26    CH.sub.3                                                                         CH.sub.3                                                                            H FCH.sub.2 (CH.sub.3).sub.2 C                                                             Cl  Cl H H                                        27    CH.sub.3                                                                         CH.sub.3                                                                            H Cl(CH.sub.3).sub.2 C                                                                     Br  H  H H 188-189                                28    CH.sub.3                                                                         CH.sub.3                                                                            H Br(CH.sub.3).sub.2 C                                                                     Br  H  H H 184.5-187                              29    CH.sub.3                                                                         CH.sub.3                                                                            H F(CH.sub.3).sub.2 C                                                                      Br  H  H H 160-163                                30    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 O(CH.sub.3).sub.2 C                                                             Br  H  H H 158-160                                31    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                     Br  H  H H 159-161                                32    CH.sub.3                                                                         CH.sub.3                                                                            H ClCH.sub.2 (CH.sub.3).sub.2 C                                                            Br  H  H H 186-188                                33    CH.sub.3                                                                         CH.sub.3                                                                            H FCH.sub.2 (CH.sub.3).sub.2 C                                                             Br  H  H H                                        34    CH.sub.3                                                                         CH.sub.3                                                                            H Cl(CH.sub.3).sub.2 C                                                                     CH.sub.3                                                                          H  H H                                        35    CH.sub.3                                                                         CH.sub.3                                                                            H Br(CH.sub.3).sub.2 C                                                                     CH.sub.3                                                                          H  H H                                        36    CH.sub.3                                                                         CH.sub.3                                                                            H F(CH.sub.3).sub.2 C                                                                      CH.sub.3                                                                          H  H H                                        37    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 O(CH.sub.3).sub.2 C                                                             CH.sub.3                                                                          H  H H                                        38    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                     CH.sub.3                                                                          H  H H                                        39    CH.sub.3                                                                         CH.sub.3                                                                            H FCH.sub.2 (CH.sub.3).sub.2 C                                                             CH.sub.3                                                                          H  H H                                        40    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.2 CH(CH.sub.3).sub.2 C                                                            Br  H  H H                                        41    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.2 CH(CH.sub.3).sub.2 C                                                            CH.sub.3                                                                          H  H H                                        42    CH.sub.3                                                                         CH.sub.3                                                                            H CH.sub.2 CH(CH.sub.3).sub.2 C                                                            Cl  Cl H H                                        43    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.2 CH                                                                      Cl  Cl H H 149-150                                44    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.3 C                                                                       Cl  Cl H H 139-142                                45    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          H  H H                                        46    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.3 C                                                                       Br  H  H H 148-150                                47    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.3 C                                                                       F   F  H H                                        48    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          CH.sub.3                                                                         H H                                        49    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H F(CH.sub.3).sub.2 C                                                                      Br  H  H H  97-100                                50    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H F(CH.sub.3).sub.2 C                                                                      CH.sub.3                                                                          H  H H                                        51    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H F(CH.sub.3).sub.2 C                                                                      Cl  Cl H H                                        52    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H F(CH.sub.3).sub.2 C                                                                      F   F  H H                                        53    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.2 CH                                                                      Br  H  H H                                        54    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.2 CH                                                                      CH.sub.3                                                                          H  H H                                        55    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H (CH.sub.3).sub.2 CH                                                                      F   F  H H                                        56    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H FCH.sub.2 (CH.sub.3).sub.2 C                                                             Br  H  H H                                        57    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H CH.sub.3 CH.sub.2 (CH.sub.3).sub.2 C                                                     Br  H  H H 144-147                                58    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                  H (CH.sub.3).sub.3 C                                                                       Br  H  H H                                        59    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                  H (CH.sub.3).sub.3 C                                                                       CH.sub.3                                                                          H  H H                                        60    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                  H F(CH.sub.3).sub.2 C                                                                      Br  H  H H                                        61    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                  H FCH.sub.2 (CH.sub.3).sub.2 C                                                             Cl  Cl H H                                        62    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                  H F(CH.sub.3).sub.2 C                                                                      CH.sub.3                                                                          H  H H                                        63    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H Br(CH.sub.3).sub.2 C                                                                     Br  H  H H 108-110                                64    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H Cl(CH.sub.3).sub.2 C                                                                     Br  H  H H 119-121                                65    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H ClCH.sub.2 (CH.sub.3).sub.2 C                                                            Br  H  H H 154-155                                66    CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   H CH.sub.3 O(CH.sub.3).sub.2 C                                                             Br  H  H H 133-134                                67    CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                  H CH.sub.3 O(CH.sub.3).sub.2 C                                                             Br  H  H H Gum                                    68    CH.sub.3                                                                         CH.sub.3                                                                               ##STR12## Br  H  H H 185-188                                 69*  CH.sub.3                                                                         CH.sub.3 CH.sub.2                                                                   CH.sub.2 C(CH.sub.3).sub.2                                                                 Br  H  H H Gum                                    __________________________________________________________________________     *Compound No 69 has the formula:                                              ##STR13##                                                                

                                      TABLE III                                   __________________________________________________________________________     ##STR14##                                                                    Compound                                                                            R.sup.1                                                                          R.sup.2                                                                          R.sup.4                                                                            A B  D E  X Y  mpt (°C.)                              __________________________________________________________________________    1     CH.sub.3                                                                         CH.sub.3                                                                         (CH.sub.3).sub.3 C                                                                 Cl                                                                              H  H H  O S  164-167                                       2     CH.sub.3                                                                         CH.sub.3                                                                         (CH.sub.3).sub.3 C                                                                 Cl                                                                              H  H H  S O  120 (dec.)                                    3     CH.sub.3                                                                         CH.sub.3                                                                         (CH.sub.3).sub.3 C                                                                 Cl                                                                              H  H H  S S  154-156                                       __________________________________________________________________________

The compounds of the invention can be made, for example, by the methodsillustrated in Schemes 1 to 11. Throughout these Schemes R¹, R², R⁴, A,B, D, and E are as defined before.

In Scheme 1, compounds of formula (II) can be prepared by reactingcompounds of formula (VI) with an acid chloride R⁴ COCl in a suitableorganic solvent such as methylene chloride or toluene in the presence ofa base such as a tertiary amine (for example triethylamine) or an alkalimetal carbonate or hydroxide (for example sodium bicarbonate or sodiumhydroxide).

Compounds of formula (VI) can be made by reduction of nitro compounds offormula (V) using standard methods known in the literature such as ironpowder in aqueous ethanol.

Amides of formula (V) can be made from compounds of formula (III) byfirst converting a compound (III) into an acid chloride of formula (IV)by treatment with a standard reagent such as thionyl chloride or oxalylchloride. The acid chloride (IV) is then reacted with an amine (R¹ R² NHin a suitable organic solvent (such as methylene chloride or toluene) orin water, in the presence of a base (such as triethylamine or sodiumbicarbonate or excess amine R¹ R² NH).

In Scheme 2, compounds of formula (II) can be prepared from compounds offormula (IX) by reaction with an amine R¹ R² NH in a suitable organicsolvent such as methylene chloride or tetrahydrofuran (THF) in thepresence of a base such as triethylamine, sodium bicarbonate or excessR¹ R² NH. ##STR15##

Acid chlorides of formula (IX) may be prepared from carboxylic acids offormula (VIII) by reaction with a standard reagent such as oxalylchloride in a suitable dry solvent such as THF or methylene chloride andwith a catalytic quantity of DMF being added if necessary.

Carboxylic acids of formula (VIII) may be prepared from theappropriately substituted 4-aminobenzoic acid (VII) by reaction with anacid chloride R⁴ COCl in water in the presence of at least twoequivalents of a base such as an alkali metal carbonate or hydroxide(for example sodium bicarbonate). The substituted 4-aminobenzoic acids(VII) can generally be made by methods described in the literature.

In Scheme 3, compounds of formula (XI) in which R⁵ and R⁶ are hydrogen,C₁₋₄ alkyl or halogen, are prepared from compounds of formula (X), inwhich X, is chlorine, bromine or iodine, by treatment with a base suchas an alkali metal hydroxide (for example sodium hydroxide) in atwo-phase system consisting of an organic solvent, such as methylenechloride, and water, in the presence of a phase-transfer catalyst (forexample tetrabutylammonium bromide).

In Scheme 4, intermediates of formula (VIII) can be made by hydrolysisof compounds of formula (XIV) by standard methods in the literature suchas treatment with aqueous mineral acid (for example aqueous sulphuricacid), or with aqueous alkali (for example aqueous sodium hydroxide withor without a cosolvent such as ethanol) or by aqueous diazotisation (forexample with sodium nitrite in aqueous sulphuric acid). Compounds offormula (XIV) can be made from compounds of formula (XIII) by hydrolysisusing standard methods in the literature such as treatment with aqueousmineral acid (for example aqueous sulphuric acid) or aqueous alkali (forexample aqueous sodium hydroxide with or without a cosolvent such asethanol) or by treatment with aqueous alkaline peroxide (for exampleaqueous hydrogen peroxide) containing sodium hydroxide with or without acosolvent such as ethanol). Compounds of formula (XIII) can be made fromcompounds of formula (XII) by reaction with an acid chloride R⁴ COCl ina suitable organic solvent (for example methylene chloride or toluene)in the presence of a base such as a tertiary amine (for exampletriethylamine) or an alkali metal carbonate or hydroxide (for examplesodium bicarbonate or sodium hydroxide). ##STR16##

In Scheme 5, intermediates of general formula (VIII) can be made byhydrolysis of an ester (XVI) where R⁷ is C₁₋₄ alkyl, with an alkalimetal hydroxide (for example sodium hydroxide) in a suitable solventsuch as water or ethanol or mixtures thereof. The ester of generalformula (XVI) can be made from an aminobenzoic acid ester of generalformula (xv) by several routes. Firstly by reaction with an acidchloride R⁴ COCl in a suitable organic solvent (for example methylenechloride or toluene) in the presence of a base such as a tertiary amine(for example triethylamine) or an alkali metal carbonate or hydroxide(for example sodium bicarbonate or sodium hydroxide). Alternatively,when any of the substituents A, B, D and E are stronglyelectron-withdrawing the amino ester (XV) can be deprotonated with astrong base (for example sodium hydride or lithium diisopropylamide) inan inert organic solvent (for example tetrahydrofuran ordimethoxyethane) and then treated with an acid chloride R⁴ COCl. Twoequivalents of strong base may be needed for satisfactory yields.Compounds of general formula (XV) can be made from compounds of generalformula (VII) by reaction with an alkanol R⁷ OH, where R⁷ is C₁₋₄ alkyl,in the presence of an acid catalyst (for example concentrated sulphuricacid or hydrogen chloride gas). ##STR17##

In Scheme 6, compounds of general formula (XVIII) where R⁸ and R⁹ areindependently H, C₁₋₄ alkyl or C₁₋₄ haloalkyl, can be made by treatmentof compounds of formula (XVII) with a fluoride transfer reagent (forexample silver tetrafluoroborate) in a suitable solvent (for exampleacetonitrile). ##STR18##

In Scheme 7 compounds of general formula (XX), where R⁸ and R⁹ are asdefined for scheme 6, can be made from hydroxy compounds of generalformula (XIX) by treatment with a fluorinating agent, (for examplediethylaminosulphur trifluoride) in a suitable solvent (for examplemethylene chloride). Compounds of general formula (xx) can also be madeby reaction of compounds of general formula (VI) with acid chlorides ofgeneral formula (XXXV), in a suitable solvent (such as methylenechloride or ethyl acetate) in the presence of a base (such astriethylamine or potassium carbonate). ##STR19##

In Scheme 8 compounds of general formula (XXI) and (XXII) can be made bytreatment of compounds of general formula (II) with a thionation reagent(for example phosphorus pentasulphide or Lawesson's reagent) in asuitable solvent (for example toluene or acetonitrile). Compounds (XXI)and (XXII) can either be produced together as a mixture, which can beseparated by chromatography or crystallisation, or compound (XXI) can beproduced alone, and can subsequently be converted to (XXII). ##STR20##

In Scheme 9 compounds of general formula (XXIV) may be made by reactionof isothiocyanates of general formula (XXIII) with organometallicreagents of type R⁴ Li, or R⁴ Mghal, where hal is a halogen such aschlorine or bromine, in a suitable solvent (such as tetrahydrofuran) ata temperature between -78° C. and +25° C.

Isothiocyanates of general formula (XXIII) can be made from compounds ofgeneral formula (VI) by standard methods, for example by treatment ofcompounds of general formula (VI) with thiophosgene.

Compounds of general formula (XXIV) can also be made from compounds ofgeneral formula (Xxv) by standard methods for making amides. For example(XXV) can be converted to an acid chloride of general formula (XXVI) bytreatment with chlorination reagents (for example oxalyl chloride orthionyl chloride), and the acid chloride (XXVI) can be reacted with anamine R¹ R² NH in the presence of a base (for example triethylamine orpotassium carbonate). The carboxylic acids of general formula (XXV) canbe made from the esters of general formula (XXVII) by hydrolysis usingstandard methods, (for example sodium hydroxide in methanol). The esters(XXVII) can in turn be made from compounds of general formula (XXVIII)by reaction with a thionation reagent (for example phosphoruspentasulphide or Lawesson's reagent) in a suitable solvent (for exampletoluene or acetonitrile).

In Scheme 10 compounds of general formula (XXXII), where R¹¹ is C₁₋₄alkyl, can be made from compounds of general formula (XIX) by reactionwith a halide R¹¹ - hal, where hal is chlorine, bromine or iodine, inthe presence of a base such as an alkali metal carbonate or oxide orhydroxide (for example barium oxide) in a suitable solvent (for examplemethanol). Compounds of general formula (XIX) can be made from compoundsof general formula (XXXI) by hydrolysis with an alkali metal hydroxide(for example sodium hydroxide) in a suitable solvent (for exampleaqueous methanol). Compounds of general formula (XXXI) ##STR21## can beprepared from compounds of general formula (VI) by reaction with acidchlorides of general formula (XXX) in a suitable solvent (for examplemethylene chloride) in the presence of a base (for exampletriethylamine). Acid chlorides of general formula (XXX) can be made bytreatment of hydroxy acids of general formula (XXXIX) with acidanhydrides of formula (R¹⁰ CO)₂ O, followed by an acid chloridegenerating reagent (for example thionyl chloride or oxalyl chloride).##STR22##

In Scheme 11 compounds of formula (II) can be prepared from compounds offormula (XXXIII), where L is a leaving group for example fluorine,chlorine, bromine, iodine, methanesulphonyloxy, p-toluenesulphonyloxy,or trifluoromethanesulphonyloxy, by reaction with a compound of generalformula R⁴ CO--NH₂ and a base (for example sodium hydride, lithiumdiisopropylamide, alkali metal alkoxides or alkali metal carbonates).Compounds of formula (II) can also be made from anilines of generalformula (VI) as described in Scheme 1. Anilines of general formula (VI)can be made by reaction of compounds of general formula (XXXIII) withammonia in a suitable. solvent (for example ethanol or pyridine).Compounds of formula (VI) can also be made from compounds of generalformula (XXXIV), where M is azido or hydrazino, by treatment with areducing agent (for example hydrogen in the presence of a catalyst).Compounds of general formula (XXXIV) can be made from compounds ofgeneral formula (XXXIII) by reaction with alkali metal azides (forexample sodium azide) or hydrazine, in suitable solvents (for exampledimethylformamide or ethanol).

In a further aspect, the invention provides processes as hereindescribed for preparing the compounds of the invention.

The compounds of the invention are active fungicides and may be used tocontrol one or more of the following pathogens:

Puccinis recondita on wheat, Erysiphe graminis (powdery mildew) onbarley, Venturia inaegualis (scab) on apples, Cercospora arachidicola onpeanuts, Plasmopara viticola on vines and Phytophthora infestans onpotatoes. In particular, they show notable activity against Plasmoparaviticola and Phytophthora infestans as systemic treatments.

The invention therefore provides a method of combating fungi whichcomprises applying to a plant, to a seed of a plant or to the locus ofthe plant or seed a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides fungicidal compositions comprisinga compound as hereinbefore defined and an acceptable carrier or diluenttherefor.

The compounds can be applied in a number of ways. For example, they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules.

Application can be to any part of the plant including the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted, or to the soil generally, to paddy water orto hydroponic culture systems. The invention compounds may also beinjected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example, fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,fuller's earth, gypsum, diatomaceous earth and china clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example, a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example, N-methylpyrrolidone, propylene glycol ordimethylformamide). The compositions may also be in the form of wettablepowders or water dispersible granules comprising wetting or dispersingagents to facilitate the dispersion in liquids. The powders and granulesmay also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbonssuch as chlorobenzene and trichlorethane, and alcohols such as benzylalcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent with a suspending agentincluded to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure of a propellant,e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.Other additives may be included to improve the biological efficacy ofthe various formulations. Such additives can be surface active materialsto-improve the wetting and retention on surfaces treated with theformulation and also the uptake and mobility of the active material, oradditionally can include oil based spray additives. For example, certainmineral oil and natural plant oil (such as soya bean and rape seed oil)additives have been found to enhance several-fold foliar protectantactivity against, for example, Plasmopara viticola.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants, e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example, sodium laurylsulphate), and salts of sulphonated aromatic compounds (for example,sodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropyl- naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonylphenol and octylcresol. other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example, polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple, etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are tetraconazole,(RS)-1-aminopropylphosphonic acid, (RS)(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-l-ylmethyl)butyronitrile,(RS)-4-chloro-N-(cyano(ethoxy)methyl)benzamide,(Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea,1-[(2RS,4RS;2RS,4RS)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl)-1H-1,2,4-triazole,3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-l-methyl)-1,3-dioxolan-2-yl]phenyl-4-chlorophenylether, 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide, 4-chlorobenzylN-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)thioacetamidate,5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxolo(4,5-g)quinoline-7-carboxylic-acid, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido)-γ-butyrolactone,anilazine, BAS 454, benalaxyl, benomyl, biloxazol, binapacryl,bitertanol, blasticidin S, bupirimate, buthiobate, captafol, captan,carbendazim, carboxin, chlorbenzthiazone, chloroneb, chlorothalonil,chlorozolinate, copper containing compounds such as copper oxychloride,copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil,cyproconazole, cyprofuram, di-2-pyridyl disulphide 1,1'-dioxide,dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran,dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos,dithianon, dodemorph, dodine, edifenphos, etaconazole, ethirimol, ethyl(Z)-N-benzyl-N-([methyl(methylthioethylideneamino-oxycarbonyl)amino]thio)-β-alaninate,etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol,fluzilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl,furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil,iprobenfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb,mepronil, metalaxyl, methfuroxam, metsulfovax, myclobutanil,N-(4-methyl-6-prop-l-ynylpyrimidin-2-yl)-aniline, neoasozin, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,organomercury compounds, oxadixyl, oxycarboxin, penconazole, pencycuron,pefurazoate, phenazin oxide, phthalide, polyoxen D, polyram,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur,pyrrolnitrin, quinomethionate, quintozene, streptomycin, sulphur,techlofthalam, tecnazene, tebuconazole, thiabendazole,thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt of1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol,triazbutyl, tricyclazole, tridemorph, triforine, validamycin A,vinclozolin and zineb. The compounds of general formula (I) can be mixedwith soil, peat or other rooting media for the protection of plantsagainst seed-borne, soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include buprofezin, carbaryl, carbofuran, carbosulfan,chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate,ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb,isoxathion, monocrotophas, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds orseedhead, formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are 3,6-dichloropicolinic acid,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, methyl-3,6-dichloroanisate, abscisic acid, asulam,benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac,ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine,hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, longchain fatty alcohols and acids, maleic hydrazide, mefluidide,morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), substituted quaternary ammonium and phosphonium compounds (e.g.chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins(e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid ornaphthoxyacetic acid), the cytokinins (e.g. benzimidazole,benzyladenine, benzylaminopurine, diphenylurea or kinetin), thegibberellins (e.g. GA₃, GA₄ or GA₇) and triapenthenol.

The following Examples illustrate the invention.

Throughout the Examples the term `ether` refers to diethyl ether,magnesium sulphate was used to dry solutions and solutions wereconcentrated under reduced presaute. Reactions involving water-sensitiveintermediates were performed under an atmosphere of nitrogen andsolvents were dried before use, where appropriate. Where shown, infraredand NMR data are selective; no attempt is made to list every absorptionin all cases. ¹ H NMR spectra were recorded using CDCl₃ solutions unlessotherwise stated. The following abbreviations are used throughout:

    ______________________________________                                        THF = tetrahydrofuran   s = singlet                                           DMF =  .sub.-- N, .sub.-- N-dimethylformamide                                                         d = doublet                                           NMR = nuclear magnetic resonance                                                                      t = triplet                                           IR = infrared           m = multiplet                                         m.p. = melting point    b = broad                                             ______________________________________                                    

EXAMPLE 1

This example illustrates the preparation of2-chloro-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide (compoundNo. 5 of Table-1).

Step 1

The preparation of 2-chloro-4-nitro-N,N-dimethylbenzamide.

2-chloro-4-nitrobenzoic acid (25.0 g) was refluxed in thionyl chloride(80 g) containing a few drops of DMF, for 3 hours. The excess thionylchloride was then evaporated and the crude 2-chloro-4-nitrobenzoylchloride added dropwise to 40% aqueous dimethylamine (70ml) at 0°-5° C.After strirring for 0.5 hour the yellow crystalline precipitate wasfiltered, washed with water and dried to give2-chloro-4-nitro-N,N-dimethylbenzamide, as a pale yellow crystallinesolid (24.97 g), m.p. 116°-117° C.

NMR (CDCl₃, 90 MHz) δ: 2.90(3H,s), 3.20(3H,s), 7.49(1H,d), 8.12(1H,d),8.27(1H,m). IR (nujol mull): 3100, 1640 cm⁻¹.

Step 2

The preparation of 4-amino-2-chloro-N,N-dimethylbenzamide.

Iron powder (pre-reduced with hydrogen, 10.0 g) was suspended in ethanol(80ml) and water (10ml) and concentrated hydrochloric acid (4ml) wereadded with vigorous stirring. 2-Chloro-4-nitro-N,N-dimethylbenzamide(7.50 g) was added in small portions over 15 minutes and the mixturethen heated to 50°-60° C. and stirred for 5 hours. The mixture wasfiltered through Celite and the ethanol evaporated. Water (200 ml) andconcentrated hydrochloric acid (20 ml) were added and the reactionwashed with ethyl acetate and then basified to pH8 with sodiumbicarbonate and extracted with methylene chloride. The organic extractwas dried and evaporated to give 4-amino-2-chloro-N,N-dimethylbenzamideas a grey crystalline solid (5.21 g) which was recrystallised fromchloroform/ethyl acetate to give off-white crystals (3.46 g, m.p. 170°173° C.).

NMR (CDCl₃, 270 MHz) δ: 2.89(3H,s), 3.11(3H,s), 3.87(2H,bs),6.57(1H,dd), 6.67(1H,s), 7.07(1H,d). IR (liquid film): 3440-3340,1640cm⁻¹.

Step 3

The preparation of2-chloro-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

4-Amino-2-chloro-N,N-dimethylbenzamide (1.0 g) and triethylamine (1.21g) were dissolved in methylene chloride (20 ml) and the solution wascooled to 0°-5° C. 2,2-Dimethylpropionyl chloride (1.21 g) was addeddropwise keeping the temperature below 100° C. and the resulting orangesolution stirred at 0°-10° C. for 0.5 hour. The organic solution wasthen washed with aqueous sodium bicarbonate and then water, dried andevaporated to give an orange solid. This was recrystallised from 3:1ethyl acetate:chloroform to give2-chloro-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide as anoff-white crystalline solid (1.027 g), m.p. 202°-203° C.

NMR (CDCl₃, 270 MHz) δ1.32(9H,s), 2.86(3H,s), 3.13(3H,s), 7.16(1H,d),7.34(1H,d), 7.68(1H,s), 7.72(1H,bs). IR (nujol mull): 3340, 1690, 1630cm⁻¹.

EXAMPLE 2

This example illustrates the preparation of2-chloro-4-(2'-methylpropionamido)-N,N-diethylbenzamide (compound No. 1of Table I).

Step 1

The preparation of 2-chloro-4-(2'-methylpropionamido)benzoic acid.

4-Amino-2-chlorobenzoic acid was stirred in water (60 ml) and1,2-dimethoxyethane (25 ml) with sodium bicarbonate (5.04 g) and thebrown suspension cooled to 0°-5° C. 2-Methylpropionyl chloride (4.26 g)was added dropwise over 10 minutes with vigorous stirring, and themixture was then stirred at 0°-10° C. for 2 hours. The mixture waspoured into 2M hydrochloric acid and the pale brown precipitate washedwith water and filtered and dried to give2-chloro-4-(2'-methylpropionamido)benzoic acid as a pale browncrystalline solid (6.30 g), m.p. 206°-209° C.

NMR (d₆ -DMSO, 270 MHz) δ: 1.05(6H,d), 2.53(1H,septet), 7.51(1H,dd),7.78(1H,d), 7.86(1H,s), 10.19(1H,s), 14-12 (1H, very bs). IR (nujolmull): 3320, 1705, 1670 cm⁻¹.

Step 2

The preparation of 2-chloro-4-(2'-methylpropionamido)-benzoyl chloride.

Oxalyl chloride (0.63 g) in dry THF (5 ml) was added dropwise over 5minutes to a solution of 2-chloro-4-(2'-methylpropionamido)benzoic acid(1.0 g) in dry THF (5 ml) at room temperature. After completion of theaddition, dry DMF (1 drop) was added causing vigorous effervescence anda slight temperature rise. After stirring for 4 hours and addition of afurther drop of DMF, the THF was evaporated to yield2-chloro-4-(2'-methylpropionamido)benzoyl chloride as a viscous browngum which was used without further purification. IR (liquid film): 3320,3260, 3160, 3070, 1780, 1710, 1680, cm⁻¹.

Step 3

The Preparation of2-chloro-4-(2'-methylpropionamido)-N,N-diethylbenzamide.

The crude 2-chloro-4-(2'-methylpropionamido)benzoyl chloride from thepreceding reaction in dry THF (10 ml) was added dropwise with stirringover 10-15 minutes to a solution of diethylamine (1.46 g) in dry THF (10ml), at 0°-5° C. After stirring at 0°-10° C. the reaction mixture wasstood overnight at room temperature, poured into cold water andextracted with ethyl acetate. This extract was dried and evaporated togive a viscous gum which crystallised slowly and was then recrystallisedfrom ethyl acetate to give2-chloro-4-(2'-methylpropionamido)-N,N-diethylbenzamide as whitecrystals (0.507 g).

NMR (CDCl₃, 270 MHz) δ: 1.04(3H,t), 1.21(6H,d), 1.26(3H,t),2.58(1H,Septet), 3.15(2H,q), 3.39(1H,bm), 3.74(1H,bm), 7.04(1H,d),7.30(1H,dd), 7.51(1H,s), 8.58(1H,bs). IR (nujol mull): 3300, 3250, 3165,1685 cm⁻¹.

EXAMPLE 3

This example illustrates the preparation of1-[3'-chloro-4'-(N,N-dimethylcarbamoyl)phenyll-3,3-dimethylazetidin-2-one(compound No. 11 of Table I).

Step 1

The preparation of2-chloro-4-(3'-chloro-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

3-Chloro-2,2-dimethylpropionyl chloride (1.86 g) was added dropwise over5 minutes to 4-amino-2-chloro-N,N-dimethylbenzamide (2.00 g) suspendedin dry methylene chloride (40 ml) and dry triethylamine (1.21 g) withstirring, keeping the temperature below 10° C. After stirring for 1 hourand warming to room temperature, methylene chloride (40 ml) was addedand the solution washed with 2M hydrochloric acid, saturated aqueoussodium bicarbonate and then saturated brine. The solution was then driedand evaporated to yield a sticky yellow solid which was recrystallisedfrom ethyl acetate/chloroform to give2-chloro-4-(3'-chloro-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide,as a white crystalline solid (2.349 g) m.p. 179°-181° C.

NMR (CDCl₃, 270 MHz) δ: 1.42(6H,s), 2.86(3H,s), 3.14(3H,s), 3.73(2H,s),7.06(1H,d), 7.26(1H,dd), 7.50(1H,s), 8.48(1H,bs). IR (nujol mull): 3310,1670, 1620 cm⁻¹.

Step 2

1-[3'-chloro-4'-(N,N-dimethylcarbamoyl)phenyl]-3,3-dimethylazetidin-2-one.

A solution of sodium hydroxide (4.00 g) and tetrabutylammonium bromide(0.10 g) in water (10 ml) was added to a suspension of2-chloro-4-(3'-chloro-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(1.00 g) in methylene chloride (10 ml) and the two-phase system stirredat room temperature for I hour. Water (10 ml) and methylene chloride (10ml) were then added and the whole methylene chloride layer washed withbrine, dried and evaporated to give a pale yellow solid. This wasrecrystallised from ethyl acetate/hexane to give1-[3'-chloro-4'-(N,N-dimethylcarbamoyl)phenyl]-3,3-dimethylazetidin-2-oneas a white crystalline solid (0.516 g), m.p. 122°-123° C.

NMR (CDCl₃, 270 MHz) δ: 1.42(6H,s), 2.87(3H,s), 3.13(3H,s), 3.46(2H,s),7.27(2H,t), 7.39(1H,s). IR (nujol mull): 3600-3100, 1740, 1625 cm⁻¹.

EXAMPLE 4

This example illustrate the preparation of2-methoxy-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide (compoundNo. 1 of Table II).

Step 1

The preparation of methyl2-methoxy-4-(2',2'-dimethylpropionamido)-benzoate.

Methyl 2-methoxy-4-aminobenzoate (3.03 g) and triethylamine (1.83 g)were stirred at 0°-5° C. in dry methylene chloride (50 ml). To thissolution was added dropwise 2,2-dimethylpropionyl chloride (6.07 g) indry methylene chloride (10 ml). After completion of the addition themixture was stirred overnight at room temperature, and poured intodilute hydrochloric acid. The organic layer was separated and washedwith dilute aqueous sodium bicarbonate and then water, and dried andevaporated to give an oil which crystallised. After heating with hexanethe product was filtered as a white solid (3.61 g).

NMR (CDCl₃, 270 MHz) δ: 1.33(9H,s), 3.86(3H,s), 3.94(3H,s), 6.79(1H,dd),7.45(1H,s), 7.79(1H,d), 7.82(1H,d).

Step 2

The preparation of 2-methoxy-4-(2',2'-dimethylpropionamido)-benzoicacid.

Methyl 2-methoxy-4-(2',2'-dimethylpropionamido)-benzoate (2.98 g) wasstirred at room temperature with potassium hydroxide (0.725 g) inmethanol (50 ml) for 3 hours, and then refluxed for 8 hours, and thenpoured into water. The mixture was extracted with ethyl acetate, andthen acidified with hydrochloric acid. This acidified fraction wasextracted with ethyl acetate and the extract was dried and evaporated togive the product as a solid (1.24 g).

NMR (CDCl₃, 270 MHz) δ: 1.36(9H,s), 4.10(3H,s), 6.78(1H,dd), 8.10(2H,m),10.61(1H,s).

Step 3

The preparation of 2-methoxy-4-(2',2'-dimethylpropionamido)-benzoylchloride.

To 2-methoxy-4-(2',2'-dimethylpropionamido)- benzoic acid (1.04 g)stirred in dry ether (25 ml) was added dropwise oxalyl chloride (1.4 g)in dry ether (5 ml) at room temperature, with a trace of DMF. Aftercompletion of the addition the mixture was stirred for 4 hours, andstood overnight. Some methylene chloride was added and the mixtureevaporated to give the acid chloride as a yellow solid (1.12 g).

Step 4

Preparation of2-methoxy-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

2-Methoxy-4-(2',2'-dimethylpropionamido)-benzoyl chloride (1.12 g) indry THF (10 ml) was added dropwise over 30 minutes to a stirred solutionof dimethylamine (1.17 g of a 40% aqueous solution) in THF (15 ml) at0°-5° C. After completion of the addition the solution was stirred for 1hour at 5°-10° C., stood at room temperature overnight, poured intowater, and extracted with ethyl acetate. The extract was dried andevaporated to give the product as a yellow solid (0.889 g), m.p.143°-144° C.

NMR (CDCl₃, 270 MHz) 8: 1.33(9H,s), 2.85(3H,s), 3.11(3H,s), 6.75(1H,dd),7.15(1H,d), 7.48(1H,s), 7.65(1H,d).

EXAMPLE 5

This example illustrates the preparation of2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(compound No. 7 of Table II).

Step 1

The preparation of2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzonitrile.

2,2-Dimethylpropionyl chloride (3.79 g) in dry methylene chloride (5 ml)was added slowly dropwise to 4-cyano-3-trifluoromethylaniline (3.02 g)and triethylamine (3.34 g) in dry methylene chloride (50 ml) at 0°-5° C.After completion of the addition the mixture was stirred at roomtemperature for 1.5 hours, and then poured into dilute hydrochloricacid. The organic fraction was washed with dilute aqueous sodiumbicarbonate, and water, and then dried and evaporated to give an orangesolid. This was recrystallised to give the product as a yellow powder.

NMR (CDCl₃, 270 MHz) δ: 1.35(9H,s), 7.61(1H,s), 7.78(1H,d), 7.93(1H,dd),8.03(1H,d). Step 2

The preparation of2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzamide.

Hydrogen peroxide (85 ml of a 30% aqueous solution) and sodium hydroxide(8.5 ml of a 20% aqueous solution were added to2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzonitrile (5.03 g)in ethanol (140 ml), and the reaction mixture was stirred for 5 days atroom temperature, during which time further ethanol (100 ml) was added.The reaction was then warmed at 50° C. for 24 hours, and was poured intowater and extracted with ethyl acetate. The organic layer was then driedand evaporated to yield an oil which was flash chromatographed on silicato give the desired product (2.89 g).

NMR (CDCl₃, 270 MHz) δ: 1.35(9H,s), 5.80(2H,bs), 7.54(1H,s), 7.59(1H,d),7.82(1H,dd), 7.90(1H,d).

Step 3

The preparation of2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzoic acid.

Concentrated hydrochloric acid (15 ml) was added to2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzamide (2.35 g) inglacial acetic acid (35 ml) at -5°--0° C. A solution of sodium nitrite(1.807 g) in water (10 ml) was then added dropwise to the mixture andthen was stirred for 1 hour at -5°--0° C. After warming to roomtemperature the reaction was stirred for 24 hours, and was poured intowater and extracted with methylene chloride. The methylene chloridefraction was washed with dilute aqueous sodium hydroxide, and thealkaline layer was acidified with dilute hydrochloric acid. Theacidified layer was extracted with methylene chloride, and the organiclayer was dried and evaporated to give the desired acid as a whitesolid, (0.926 g).

NMR (CDCl₃, 270 MHz) δ: 1.20(9H,s), 7.79(1H,d), 8.02(1H,dd), 8.19(1H,d),9.69(1H,s).

Step 4

The preparation of2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

Oxalyl chloride (0.64 g) in dry ether (7 ml) was added dropwise withstirring to 2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzoicacid (0.926 g) in dry ether (40 ml) at room temperature. A drop of DMFwas added during the addition. After two hours further oxalyl chloride(0.257 g) was added and the reaction stirred for a further two hours.The organic solution was then decanted from a precipitate, andevaporated to yield2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-benzoyl chloride as aliquid (1.136 g), which was used without purification.

The acid chloride (1.136 g) in dry THF (10 ml) was added dropwise withstirring over 30 minutes to dimethylamine (1.0 g of a 40% aqueoussolution) in THF (15 ml) at 0°-5° C. The reaction was allowed to warm toroom temperature and stood for 21/2 days, and then poured into water,and extracted with ethyl acetate. The ethyl acetate fraction was washedwith aqueous sodium bicarbonate, followed by dilute hydrochloric acidand then water. After being dried, the organic solution was evaporatedto give2-trifluoromethyl-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide,as a white solid (0.576 g), m.p. 198.7°-199.6° C.

NMR (CDCl₃, 270 MHz) δ: 1.35(9H,s), 2.80(3H,s), 3.12(3H,s), 7.22(1H,d),7.72(1H,s), 7.75(1H,dd), 7.85(1H,d).

EXAMPLE 6

This example illustrates the preparation of2,3,5,6-tetrafluoro-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(compound No. 6 of Table II).

Step 1

The preparation of methyl2,3,5,6-tetrafluoro-4-(2',2'-dimethylpropionamido)-benzoate.

Methyl 2,3,5,6-tetrafluoro-4-aminobenzoate (1.887 g) in dry THF (5 ml)was added to a suspension of sodium hydride (0.764 g of a 55% dispersionin oil) in dry THF (70 ml) stirred at room temperature. After completionof the effervescence, 2,2-dimethylpropionyl chloride (1.127 g) in dryTHF (5 ml), was slowly added dropwise with cooling. The reaction wasstirred at 10° C. for I hour and then poured into water, and extractedwith ethyl acetate. The ethyl acetate fraction was washed with dilutehydrochloric acid and dilute aqueous sodium bicarbonate, dried andevaporated to give the product as a white solid, (2.44 g).

NMR (CDCl₃, 270 MHZ) δ: 1.36(9H,s), 3.97(3H,s), 7.05(1H,s).

Step 2

The preparation of2,3,5,6-tetrafluoro-4-(2',2'-dimethylpropionamido)-benzoic acid.

Methyl 2,3,5,6-tetrafluoro-4-(2',2'-dimethylpropionamido)-benzoate (1.83g), was stirred overnight with potassium hydroxide (0.669 g dissolved inthe minimum quantity of water) in dimethoxyethane (DME) (60 ml), and wasthen poured into water. The mixture was extracted with ethyl acetate.The aqueous phase was acidified and extracted with ethyl acetate, andthis ethyl acetate extract was dried and evaporated to give the acid asa pale yellow solid (1.538 g).

NMR (CDCl₃, 270 MHz) δ: 1.19(9H,s), 9.65(1H,s).

Step 3

The preparation of2,3,5,6-tetrafluoro-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

Oxalyl chloride (1.00 g) in dry ether (5 ml) was added dropwise, withstirring to 2,3,5,6-tetrafluoro-4-(2',2'-dimethylpropionamido)-benzoicacid (1.47 g) in dry ether (35 ml), to which a drop of DMF had beenadded. After stirring for 2 hours at room temperature, the ethersolution was decanted from insoluble material and evaporated to give theacid chloride as an oil (1.494 g), which was used without purification.

The acid chloride (1.494 g) in dry THF (10 ml) was slowly added dropwiseover 30 minutes to dimethylamine (1.363 g) in THF (10 ml) at 0°-5° C.After stirring at 10° C. for 1.5 hours the reaction mixture was pouredinto water, and extracted with ethyl acetate. The extract was washedwith aqueous sodium bicarbonate, and then dilute hydrochloric acid,dried and evaporated to give the product as a white powdery solid (1.279g), m.p. 187°-189° C.

NMR (CDCl₃, 270 MHz) δ: 1.35(9H,s), 2.97(3H,s), 3.17(3H,s), 7.82(1H,s).

EXAMPLE 7

This example illustrates the preparation of2-chloro-4-(2'-fluoro-2'-methylpropionamido)-N,N-dimethylbenzamide(compound No 38 of Table I).

Silver tetrafluoroborate (0.60 g) in acetonitrile (5 ml) was added to2-chloro-4-(2'-bromo-2'-methylpropionamido)-N,N-dimethylbenzamide (1.065g) in acetonitrile (150 ml) and the reaction mixture stirred undernitrogen, protected from light, for 6.5 hours. Ethyl acetate was addedand the solution was filtered through celite and evaporated. The residuewas dissolved inn ethyl acetate again and filtered through celite andevaporated. The residue was purified by HPLC (eluent methylene chloride:acetonitrile, 2:1) to give the product as a white crystalline solid(0.319 g), m.p. 125°-128° C.

NMR (CDCl₃, 270 MHz) δ: 1.67(6H,d), 2.87(3H,s), 3.13(3H,s), 7.27(1H,d),7.45(1H,dd), 7.80(1H,d), 8.18(1H,d).

EXAMPLE 8

This Example illustrates the preparation of2-chloro-4-(3'-fluoro-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(compound 42 of Table I).

Step 1

The preparation of2-chloro-4-(3'-acetoxy-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

3-Acetoxy-2,2-dimethylpropionyl chloride (7.84 g) was added to a stirredsolution of 4-amino-2-chloro-N,N-dimethylbenzamide (5.88 g) andtriethylamine (5.99 g) in dry methylene chloride (15 ml) at 0°-5° C.After stirring for 30 minutes the reaction mixture was washed withdilute aqueous sodium bicarbonate, dilute sodium hydroxide, dilutehydrochloric acid, and then water. The organic layer was dried andevaporated to give an orange solid, which was triturated with hexane togive the desired product (9.08 g), m.p. 117°-120° C.

NMR (CDCl₃, 270 MHz) δ: 1.33(6H,s), 2.10(3H,s), 2.86(3H,s), 3.13(3H,s),4.20(2H,s), 7.11(1H,d), 7.29(1H,dd), 7.60(1H,d), 8.21(1H,s).

IR (nujol mull) 1740, 1680, 1630 cm⁻¹

Step 2

The preparation of2-chloro-4-(3'-hydroxy-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

2-Chloro-4-(3'-acetoxy-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(8.14 g) was stirred in methanol (100 ml) containing potassium hydroxide(2.68 g) at room temperature for 2 hours. The methanol was evaporatedand the residue extracted with ethyl acetate. The ethyl acetate wasdried and evaporated to give the desired product, (5.03 g), m.p.137°-139° C.

NMR (CDCl₃, 270 MHz) δ: 1.17(6H,s), 2.89(3H,s), 3.15(3H,s), 3.56(3H,d),5.12(1H,t), 7.17(1H,d), 7.30(1H,dd), 7.69(1H,d), 9.49(1H,s).

Step 3

The preparation of2-chloro-4-(3'-fluoro-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide.

2-Chloro-4-(3'-hydroxy-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(1.008 g) in dry methylene chloride (40 ml), was added dropwise over 3hours to a solution of diethylaminosulphur trifluoride (DAST) (0.68 g)in dry methylene chloride (20 ml) at -70° C. After 1/2 hour, a furtheramount of DAST (0.128 g) was added and the solution stirred at -70° Cfor 1/2 hour, and then warmed to room temperature overnight. Thereaction mixture was washed with water, dried and evaporated to give afoam. This was triturated with hexane to give the desired product as apale orange powder (0.269 g), m.p. 152°-4° C.

NMR (CDCl₃, 270 MHz) δ: 1.32(6H,d), 2.86(3H,s), 3.12(3H,s), 4.48(2H,d),7.23(1H,d), 7.39(1H,dd), 7.75(1H,d), 7.77(1H,s).

EXAMPLE 9

This Example illustrates the preparation of2-chloro-4-(3'-methoxy-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide,(compound 40 of Table I).

Barium oxide (2.608 g) and barium hydroxide (0.540 g) were added to asolution of2-chloro-4-(3'-hydroxy-2',2'-dimethylpropionamido)-N,N-dimethylbenzamide(0.510 g) in DMF (20 ml) at 0° C. After stirring at 0° C. for 15 minutesmethyl iodide (3.64 g) was added dropwise. After allowing to warm toroom temperature over 2 hours methylene chloride was added to thereaction and then the mixture was filtered through celite. The organicfraction was dried and evaporated to give a mobile liquid which waspurified by HPLC (eluent: ethyl acetate) to give the desired product asa solid (0.101 g), m.p. 101°-103° C.

NMR (CDCl₃, 270 MHz) δ: 1.24(6H,s), 2.86(3H,s), 3.12(3H,s), 3.43(2H,s),3.51(3H,s), 7.21(1H,d), 7.39(1H,dd), 7.75(1H,d), 9.05(1H,s).

EXAMPLE 10

This Example illustrates the preparation of2-chloro-4-(2',2'-dimethyl-thiopropionamido)-N,N-dimethyl-thiobenzamideand 2-chloro-4-(2',2'-dimethylpropionamido)-N,N-dimethyl-thiobenzamide(compounds 3 and 1 respectively, of Table III).

2-Chloro-4-(2',2'-dimethylpropionamido)-N,N-dimethylbenzamide (1.00 g)was suspended in dry toluene (10 ml) and Lawesson's reagent (0.73 g) wasadded in small portions over 5 minutes, at room temperature. Thesuspension was refluxed for 1 hour, giving a clear solution, and thetoluene was then evaporated to give a viscous gum, which waschromatographed on silica gel (eluent:methylene chloride) to give thetwo products:

1.2-chloro-4-(2',2'-dimethyl-thiopropionamido)-N,N-dimethyl-thiobenzamide(0.104 g), m.p. 154°-156° C.

NMR (CDCl₃, 270 MHz) δ: 1.47(9H,s), 3.14(3H,s), 3.60(3H,s), 7.29(1H,d),7.52(1H,dd), 7.82(1H,s), 8.85(1H,bs).

2. 2-chloro-4-(2',2'-dimethylpropionamido)-N,N-dimethyl-thiobenzamide(0.475 g), m.p. 164°-167° C.

NMR (CDCl₃, 270 MHz) δ: 1.31(9H,s), 3.11(3H,s), 3.58(3H,s), 7.25(1H,d),7.33(1H,dd), 7.38(1H,bs), 7.74(1H,s).

EXAMPLE 11

This Example illustrates the preparation of2-chloro-4-(2',2'-dimethyl-thiopropionamido)-N,N-dimethylbenzamide(compound 2 of Table 3).

Step 1

The preparation of 3-chloro-4-N,N-dimethylcarbamoylphenylisothiocyanate.

Thiophosgene (1.15 g) was added dropwise over 3 minutes to sodiumbicarbonate (1.68 g) suspended and stirred in water at room temperature.4-Amino-2-chloro-N,N-dimethylbenzamide (1.00 g) was then addedportionwise over 20 minutes, keeping the temperature at 20°-25° C. Aftera further 15 minutes the brown suspension was extracted with methylenechloride, and the organic layer dried and evaporated to give the desiredproduct as an orange-yellow solid (1.18 g), which was used withoutfurther purification.

NMR (CDCl₃, 270 MHz) δ: 2.86(3H,s), 3.13(3H,s), 7.17(1H,dd), 7.26(1H,s),7.28(1H,d).

IR (nujol mull): 2140-2080(bs), 1630 cm⁻.

The preparation of2-chloro-4-(2',2'-dimethyl-thiopropionamido)-N,N-dimethylbenzamide.

Tertiary-butyl lithium (3.2 ml of a 1.7M solution in pentane) was addedover 20 minutes to a stirred solution of3-chloro-4-N,N-dimethylcarbamoylphenyl isothiocyanate (1.17 g) in THFunder nitrogen at -70° C. After stirring for 20 minutes at the sametemperature water was carefully added followed by concentratedhydrochloric acid. The mixture was extracted with methylene chloride,which was then dried and evaporated to give a sticky brown solid (1.23g). This was purified by HPLC (eluent:ethyl acetate) to give a yellowgum (0.099 g). Trituration with ether/toluene gave the desired productas a yellow solid, m.p. 120° C. (dec.).

NMR (CDCl₃, 270 MHz) δ: 1.66(9H,s), 2.88(3H,s), 3.14(3H,s), 7.25(1H,d),7.45(1H,dd), 7.64(1H,d), 8.82(1H,bs).

EXAMPLE 12

This Example illustrates the preparation of2-chloro-4-(2',2'-dimethylpent-4'-ynamido)-N,N-dimethylbenzamide(compound 66 of Table I).

Step 1

The preparation of ethyl 2,2-dimethylpent-4-ynoate.

Lithium diisopropylamide (13.7 ml of a 1.5M solution of the mono-THFcomplex in cyclohexane) was added dropwise over 20 minutes to a stirredsolution of ethyl isobutyrate (2.38 g) in dry THF (10 ml) under nitrogenkeeping the temperature below -60° C. After 1 hour propargyl bromide(2.45 g) in dry THF (5 ml) was added dropwise, keeping the temperaturebelow -60° C. The reaction was allowed to warm to room temperature over2 hours and was then poured into water and extracted with ethyl acetate.The ethyl acetate fraction was dried and evaporated to give anorange-brown liquid, which was distilled (Kugelrohr, 115° C./60mm) togive the desired product (1.39 g).

NMR (CDCl₃, 270 MHz) δ: 1.19(3H,t), 1.21(6H,s), 1.93(1H,t), 2.38(2H,d),4.08(2H,q).

Step 2

The preparation of 2,2-dimethylpent-4-ynoic acid.

Ethyl 2,2-dimethylpent-4-ynoate (1.39 g) was stirred with potassiumhydroxide (1.07 g) in methanol (20 ml) for 71/2 hours at 40° C., andthen stood overnight. The reaction was poured into water, and washedwith ethyl acetate. The aqueous layer was acidified and extracted withethyl acetate. This layer was then dried and evaporated to give thedesired acid as a liquid (1.05 g).

NMR (CDCl₃, 270 MHz) δ: 1.32(6H,s), 2.04(1H,t), 2.47(2H,d).

IR (liquid film) 3300, 3000-2500, 1720 cm⁻.

Step 3

The preparation of2-chloro-4-(2',2'-dimethyl-pent-4-ynamido)-N,N-dimethylbenzamide.

2,2-Dimethylpent-4-ynoic acid was stirred in dry ether (15 ml) at roomtemperature while oxalyl chloride (1.53 g) in dry ether (5 ml) was addeddropwise with stirring. After completion of the addition the mixture wasstirred for 1/2 hour.

The mixture was decanted and the ether evaporated to give the acidchloride (0.417 g) as a pale liquid which was used without furtherpurification.

To a stirred solution in methylene chloride of4-amino-2-chloro-N,N-dimethylbenzamide (0.524 g) and triethylamine(0.534 g) was added 2,2-dimethylpent-4-ynoic carboxylic acid chloride(0.417 g) at 0°-5° C. After stirring for 11/2 hours, the reactionmixture was washed with dilute hydrochloric acid, aqueous sodiumbicarbonate and water. The methylene chloride solution was dried andevaporated to give a foam which crystallised to give the desired productas a pale orange solid (0.606 g), m.p. 154°-5° C.

NMR (CDCl₃, 270 MHz) δ: 1.40(6H,s), 2.17(1H,t), 2.52(2H,d), 2.87(3H,s),3.13(3H,s), 7.05(1H,d), 7.33(1H,dd), 7.64(1H,d).

The following are examples of compositions suitable for agricultural andhorticultural purposes which can be formulated from the compounds of theinvention. Such compositions form another aspect of the invention.Percentages are by weight.

EXAMPLE 13

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No. 1 of Table I   10%                                               Benzyl alcohol              30%                                               Calcium dodecylbenzenesulphonate                                                                          5%                                                Nonylphenolethoxylate (13 mole ethylene oxide)                                                            10%                                               Alkyl benzenes              45%                                               ______________________________________                                    

EXAMPLE 14

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed on to the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 2 of Table I                                                                              5%                                                   Attapulgite granules     95%                                                  ______________________________________                                    

EXAMPLE 15

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No. 3 of Table I                                                                              50%                                                  Mineral oil              2%                                                   China clay               48%                                                  ______________________________________                                    

EXAMPLE 16

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No. 4 of Table I                                                                              5%                                                   Talc                     95%                                                  ______________________________________                                    

EXAMPLE 17

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No. 5 of Table I                                                                              40%                                                  Sodium lignosulphonate   10%                                                  Bentonite clay           1%                                                   Water                    49%                                                  ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 18

A wettable powder formulation is made by mixing together and grindingthe ingredients until all are thoroughly mixed.

    ______________________________________                                        Compound No. 6 of Table I                                                                              25%                                                  Sodium lauryl sulphate   2%                                                   Sodium lignosulphonate   5%                                                   Silica                   25%                                                  China clay               43%                                                  ______________________________________                                    

EXAMPLE 19

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No. 1 or 2) in 4cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed onto the foliage and applied to theroots of the plants in the soil. The sprays were applied to maximumretention and the root drenches to a final concentration equivalent toapproximately 40 ppm a.i. in dry soil. Tween 20, to give a finalconcentration of 0.05%, was added when the sprays were applied tocereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace-5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease untreated plants

The results are shown in Tables IV, V and VI.

                                      TABLE IV                                    __________________________________________________________________________    Compound                                                                            Puccinia                                                                           Erysiphe                                                                           Venturia                                                                            Cercospora                                                                           Plasmopara                                                                          Phytophthora                               No.   Recondita                                                                          Graminis                                                                           Inaequalis                                                                          Arachidicola                                                                         Viticola                                                                            Infestans                                  (Table I)                                                                           (Wheat)                                                                            (Barley)                                                                           (Apples)                                                                            (Peanut)                                                                             (Vines)                                                                             (Tomatoes)                                 __________________________________________________________________________    1     2    0    0     0      4     3                                          2     2    0    1     0      4     4                                          3     0    0    0     0      0     4                                          4     3    1    4     --     4     3                                          5     4    0    4     2      4     4                                          6     3    2    4     0      4     2                                          7     3    4    --    0      3     0                                          8     2    0    4     4      3     1                                          9     0    0    0     1      4     1                                          10    0    0    0     0      4     4                                          11    0    0    3     0      4     4                                          12    0    0    0     0      4     4                                          13    4    1    --    --     4     4                                          14    4    0    --    0      4     4                                          15    3    0    --    1      4     4                                          16    0    0    0     0      4     4                                          17    0    0    4     2      4     4                                          18    0    2    0     0      4     4                                          19    0    2    0     0      4     4                                          20    0    0    0     0      4     4                                          21    0    0    2     0      4     4                                          22    0    0    0     0      0     3                                          23    2    0    0     0      4     2                                          24    4    1    3     --     4     4                                          25    0    1    4     0      --    3                                          26    0    0    0     3      4     3                                          27    0    0    0     2      4     0                                          28    0    0    0     3      4     0                                          29    3    0    4     0      4     4                                          30    2    0    0     2      4     4                                          31    0    0    0     0      4     4                                          32    1    0    2     0      3     4                                          33    2    1    4     0      4     4                                          34    0    0    0     3      4     4                                          35    0    0    4     3      4     3                                          36    0    3    0     0      3     0                                          37    0    0    4     0      4     0                                          38    0    0    0     --     4     4                                          40    0    0    2     --     3     3                                          66    0    0    0     --     4     4                                          67    0    0    0     0      3     3                                          68    3    2    --    3      3     3                                          __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________    Compound                                                                            Puccinia                                                                           Erysiphe                                                                           Venturia                                                                            Cercospora                                                                           Plasmopara                                                                          Phytophthora                               No.   Recondita                                                                          Graminis                                                                           Inaequalis                                                                          Arachidicola                                                                         Viticola                                                                            Infestans                                  (Table II)                                                                          (Wheat)                                                                            (Barley)                                                                           (Apples)                                                                            (Peanut)                                                                             (Vines)                                                                             (Tomatoes)                                 __________________________________________________________________________    1     0    0    0     0      0     4                                          2     0    1    0     0      --    4                                          3     0    0    0     0      4     3                                          4     0    0    0     0      4     4                                          5     0    --   0     --     4     4                                          6     0    0    0     2      3     0                                          7     0    0    0     --     4     3                                          __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________    Compound                                                                            Puccinia                                                                           Erysiphe                                                                           Venturia                                                                            Cercospora                                                                           Plasmopara                                                                          Phytophthora                               No.   Recondita                                                                          Graminis                                                                           Inaequalis                                                                          Arachidicola                                                                         Viticola                                                                            Infestans                                  (Table II)                                                                          (Wheat)                                                                            (Barley)                                                                           (Apples)                                                                            (Peanut)                                                                             (Vines)                                                                             (Tomatoes)                                 __________________________________________________________________________    1     2    0    --    --     4     0                                          3     2    2    --    --     4     0                                          __________________________________________________________________________

We claim:
 1. A compound of the formula (I): ##STR23## in which A and Bare independently H, fluoro, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy orhalo(C₁₋₁₄)alkyl provided that both are not H; D and E are independentlyH or fluoro; R¹ is C₁₋₄ alkyl or C₁₋₄ alkoxy; R² is C₁₋₄ alkyl or C₁₋₄alkoxy; R³ is H; R⁴ is trichloromethyl, C₂₋₈ alkyl or C₂₋₈ alkylsubstituted with halogen, C₁₋₈ alkoxy or R'S(O)_(n) in which R¹ is C₁₋₄alkyl, C₂₋₄ alkenyl or C₂₋₄ alkynyl and n is 0, 1 or 2, cyclopropyl orcyclopropyl substituted with halogen or C₁₋₄ alkyl, C₂₋₈ alkenyl, C₂₋₈alkynyl or C₂₋₈ alkoxy; and X and Y are both oxygen.
 2. A compoundaccording to claim 1 in which A and B are independently H, fluoro,chloro or bromo provided that both are not H; D and E are both H; R¹ isC₁₋₄ alkyl; R² is C₁₋₄ alkyl or C₁₋₄ alkoxy; R³ is hydrogen; R⁴ is C₃₋₆alkyl, C₃₋₆ alkyl substituted with halogen, methoxy, methylthio ormethylsulphonyl, cyclopropyl, cyclopropyl substituted with methyl, C₃₋₆alkenyl, C₃₋₆ alkynyl or C₁₋₄ alkoxy; and X and Y are both oxygen.
 3. Acompound according to claim 1 in which A is chloro; B, D and E are allH; R¹ is methyl or ethyl; R² is methyl or ethyl; R³ is hydrogen; R⁴ isC₃₋₄ alkyl or cyclopropyl; and X and Y are both oxygen.
 4. A compoundaccording to claim 1 in which A is chloro; B, D and E are all H; R¹ andR² are independently methyl or ethyl; R³ is hydrogen; R⁴ is iso-propyl,t-butyl or cyclopropyl; and X and Y are both oxygen.
 5. A compound ofthe formula (I.1): ##STR24## in which A is chloro, bromo or methyl; B isH, chloro, bromo or methyl; and Z is fluoro, chloro, bromo, methyl,ethyl or methoxy.
 6. A compound according to claim 5 in which A ischloro, bromo or methyl and B is H, or A and B are both chloro or bothmethyl.
 7. A compound according to claim 5 in which A is chloro or bromoand B is H, or A and B are both chloro; and Z is methyl.
 8. A fungicidalcomposition comprising a fungicidally effective amount of a compoundaccording to claim 1 and a fungicidally acceptable carrier or diluenttherefor.
 9. A compound according to claim 1 wherein R¹ is H, C₁₋₄ alkylor C₁₋₄ alkoxy; R² is C₁₋₄ alkyl, C₁₋₄ alkoxy or optionally substitutedphenyl; R⁴ is trichloromethyl, C₂₋₈ alkyl optionally substituted withhalogen, C₁₋₈ alkoxy or R'S(O)_(n) in which R' is C₁₋₄ alkyl, C₂₋₄alkenyl or C₂₋₄ alkynyl and n is 0, 1 or 2, cyclopropyl optionallysubstituted with halogen or C₁₋₄ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkynyl orC₂₋₈ alkoxy; and X and Y are oxygen.
 10. A compound according to claim 1wherein A is chlorine; B, D and E are hydrogen; Y and X are both oxygen;R¹ and R² are both methyl; R³ is hydrogen and R⁴ is --C(CH₃)₂ F.